Plasticizer composition

ABSTRACT

The present disclosure relates to a plasticizer composition that is environmentally friendly by including a recycled raw material, and has excellent gelling properties, plasticization efficiency, and weather resistance.

CROSS CITATION WITH RELATED APPLICATION(S)

The present application is based on, and claims priority from, KoreanPatent Application No. 10-2020-0186414, filed on Dec. 29, 2020, thedisclosures of which are hereby incorporated by reference herein intheir entirety.

TECHNICAL FIELD

The present disclosure relates to a plasticizer composition including arecycled raw material.

BACKGROUND

Recently, for environmental protection and resource recycling, researchhas been conducted to recover useful resources from waste syntheticresins or by-products generated in the production of synthetic resins.In addition, research to reduce carbon emissions generated in theproduction of synthetic resin products is being actively conducted.

As a recycling technology of waste synthetic resins, in particular, amethod of recycling waste polyesters is widely known. For example, amethod of depolymerizing waste polyesters in the presence of a catalystto recycle them into terephthalic acid, dimethyl terephthalate, andethylene glycol as raw materials is known. The recycled terephthalicacid and dimethyl terephthalate may be recycled into dioctylterephthalate, which is a useful material as a plasticizer, throughesterification or transesterification. In addition, Chinese PatentPublication Nos. 104230714 and 104496819 disclose a method of recoveringdioctyl terephthalate from wastewater in a polyester weight deductionprocess.

Dioctyl terephthalate is a widely used plasticizer, and dioctylterephthalate recovered through the recycling process may also be usedas a plasticizer for polymer resins. However, the recycled dioctylterephthalate has disadvantages such as a yellow color and a foul smellcompared to pure dioctyl terephthalate due to impurities mixed in duringthe recycling process. Accordingly, there is a problem in that therecycled dioctyl terephthalate can be used only in the manufacture ofrelatively low-quality products.

Therefore, it is required to develop a plasticizer composition capableof obtaining the effect of reducing carbon emissions in the resourcerecycling and manufacturing processes with excellent quality.

BACKGROUND ART LITERATURE Patent Literature

(Patent Literature 0001) Chinese Patent Publication No. 104230714

(Patent Literature 0002) Chinese Patent Publication No. 104496819

DETAILED DESCRIPTION OF THE INVENTION Technical Problem

In the present disclosure, there is provided a plasticizer compositionhaving excellent physical properties while including a recycledphthalate-based compound obtained from waste polyester or wastewatergenerated in the production of a polyester.

Technical Solution

According to one embodiment of the present disclosure, there is provideda plasticizer composition, including

a) a recycled phthalate-based compound as a first plasticizer; and

b) a citrate-based compound as a second plasticizer,

wherein the first plasticizer is included in an amount of 90 parts byweight or less based on 100 parts by weight of the plasticizercomposition.

According to another embodiment of the present disclosure, there isprovided a resin composition including the above plasticizercomposition; and at least one resin selected from the group consistingof polyvinyl chloride, polystyrene, polyurethane, polypropylene,polybutadiene, silicone, modified silicone, ethylene vinyl acetateresin, and thermoplastic elastomer.

According to another embodiment of the present disclosure, there isprovided a molded product including the above resin composition.

Advantageous Effects

The plasticizer composition according to the present disclosure includesa recycled raw material, but has little yellow color and odor withexcellent plasticization efficiency, a fast gelling rate, lowplasticizer migration characteristics, and excellent weather resistance,so that it can be used as a general-purpose plasticizer.

Detailed Description of the Embodiments

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention.The singular forms are intended to include the plural forms as well,unless the context clearly indicates otherwise.

As the present invention can be variously modified and have variousforms, specific embodiments thereof are shown by way of examples andwill be described in detail. However, it is not intended to limit thepresent invention to the particular form disclosed and it should beunderstood that the present invention includes all modifications,equivalents, and replacements within the idea and technical scope of thepresent invention.

Hereinafter, the plasticizer composition, the resin compositionincluding the same, and the molded product of the present invention willbe described in more detail.

Plasticizer Composition First Plasticizer

The plasticizer composition of the present disclosure includes arecycled phthalate-based compound as the first plasticizer.

In the present disclosure, the recycled phthalate-based compound refersto a phthalate-based compound that is not synthesized from pure rawmaterials, but is recovered from wastes through reprocessing.

Herein, the phthalate-based compound refers to a compound represented bythe following Chemical Formula 1:

in Chemical Formula 1,

R₁ and R₂ are each independently a C4 to C12 linear or branched alkylgroup.

Preferably, R₁ and R₂ may each independently be n-butyl, n-hexyl,n-octyl, 2-ethylhexyl, isononyl, or isodecyl.

The phthalate-based compound of Chemical Formula 1 may be represented bythe following Chemical Formulae 1-1 to 1-3 depending on the position ofthe substituent.

in Chemical Formulae 1-1 to 1-3, R₁ and R₂ are as defined in ChemicalFormula 1.

The Chemical Formula 1-1 is a phthalate compound, the Chemical Formula1-2 is an isophthalate compound, and the Chemical Formula 1-3 is aterephthalate compound.

Specific example of the phthalate compound represented by the ChemicalFormula 1-1 may be dibutyl phthalate (DBP), dihexyl phthalate (DHP),dioctyl phthalate (DOP; or di(2-ethylhexyl)phthalate), di-n-octylphthalate (DnOP), diisononyl phthalate, or diisodecyl phthalate (DIDP).

Specific example of the isophthalalate compound represented by theChemical Formula 1-2 may be dibutyl isophthalalate (DBIP), dioctylisophthalate (DOIP; or di(2-ethylhexyl)isophthalate), diisononylisophthalate (DINIP), or diisodecyl isophthalate (DIDIP).

Specific example of the terephthalate compound represented by theChemical Formula 1-3 may be dibutyl terephthalate (DBTP), dioctylterephthalate (DOTP; or di(2-ethylhexyl)terephthalate), diisononylterephthalate (DINTP), or diisodecyl terephthalate (DIDTP).

The recycled phthalate-based compound of the present disclosure may beany one or a mixture of the above-described phthalate compound,isophthalate compound, and terephthalate compound. Preferably, recycleddioctyl terephthalate may be used as the recycled phthalate-basedcompound.

The recycled phthalate-based compound used in the present disclosure maybe a commercially available product, or may be obtained from wastesusing by using a known method.

For example, the recycled phthalate-based compound may be obtained bydepolymerizing waste polyesters to obtain an aromatic dicarboxylic acidor an ester thereof, and reacting it with appropriate alcohol.

Alternatively, phthalic acid is extracted from wastewater dischargedduring caustic reduction processing of polyester fibers, wastewatergenerated in the production of pure terephthalate-based compounds, andwastes such as residues after filtration, and reacted with alcohol toobtain recycled phthalate-based compounds.

In the present disclosure, the recycled phthalate-based compound isincluded in an amount of 90 parts by weight or less based on 100 partsby weight of the total plasticizer composition.

Recycled phthalate-based compounds have a yellow color and a foul smelllike oil due to impurities mixed in during the recycling process fromwastes. In addition, the recycled phthalate-based compound often has ahigh acid value. Due to these problems, the recycled phthalate-basedcompound has a problem in that it is difficult to apply it in themanufacture of high-quality products in which color or smell isimportant.

Accordingly, the present disclosure controls the content of the recycledphthalate-based compound to 90 parts by weight or less based on 100parts by weight of the plasticizer composition and uses a citrate-basedcompound together with the recycled phthalate, thereby solving color andodor problems derived from the recycled phthalate-based compound.

Preferably, the first plasticizer, that is, the recycled phthalate-basedcompound may be included in an amount of 88 parts by weight or less, 86parts by weight or less, 85 parts by weight or less, 83 parts by weightor less, or 80 parts by weight or less, and 15 parts by weight or more,20 parts by weight or more, 25 parts by weight or more, 30 parts byweight or more, 35 parts by weight or more, 40 parts by weight or more,45 parts by weight or more, or 50 parts by weight or more based on 100parts by weight of the plasticizer composition.

As described above, since the plasticizer composition of the presentdisclosure includes a pure citrate-based compound, not a recycled rawmaterial, as a second plasticizer together with the first plasticizer,it is possible to supplement the disadvantages of using a recycled rawmaterial. Accordingly, physical properties of the recycledphthalate-based compound used in the present disclosure are notparticularly limited, but it may be more preferable to use a recycledphthalate-based compound having a low acid value in order to obtain ahigh-quality plasticizer.

Specifically, in order to improve the quality of the plasticizer, theacid value of the recycled phthalate-based compound is preferably 0.2KOH mg/g or less, 0.18 KOH mg/g or less, 0.15 KOH mg/g or less, or 0.12KOH mg/g or less. There is no specific lower limit, because the loweracid value can be evaluated as the better. In theory, the lower limitmay be 0 KOH mg/g. However, as described above, the recycledphthalate-based compound has a higher acid value than that of a pureplasticizer, and the acid value of the recycled phthalate-based compoundmay be 0.05 KOH mg/g or more, 0.06 KOH mg/g or more, 0.08 KOH mg/g ormore, 0.09 KOH mg/g or more, or 0.1 KOH mg/g or more. In particular,when the acid value of the first plasticizer is high, the color of thecomposition may change from colorless and transparent to yellow orbrown, or the odor may be severe. Alternatively, since there is apossibility that migration resistance of the final product using theplasticizer having a high acid value is inferior, it is preferable thatthe first plasticizer maintains the acid value within the above range.

Herein, the acid value is a weight (mg) of potassium hydroxide (KOH)required to neutralize the acid contained in 1 g of a sample, and can beobtained by titrating the sample solution with an alcoholic KOH solutionhaving a concentration of 0.1 N.

Second Plasticizer

The plasticizer composition of the present disclosure includes acitrate-based compound as a second plasticizer. The citrate-basedcompound is prepared from a pure raw material, and can supplement thecharacteristics of the recycled phthalate-based compound, which is thefirst plasticizer, such as high acid value, color, and odor. Inaddition, it is used together with the first plasticizer to improvethermal stability of the plasticizer composition, and enhanceplasticization efficiency, plasticizer migration characteristics, andgelling rate.

The citrate-based compound is represented by the following ChemicalFormula 2:

in Chemical Formula 2,

R″₁, R″₂, and R″₃ are each independently a C2 to C12 linear or branchedchain alkyl group, and

R″₄ is hydrogen or an acetyl group.

Preferably, R″₁, R″₂, and R″₃ are each independently a butyl group, anisobutyl group, a pentyl group, a hexyl group, a heptyl group, a2-ethylhexyl group, an octyl group, a nonyl group, an isononyl group, a2-propylheptyl group, a decyl group, an isodecyl group, or a stearylgroup. Preferably, R″₁, R″₂, and R″₃ are each independently a butylgroup, a 2-ethylhexyl group, or an isononyl group.

The citrate-based compound of Chemical Formula 2 may be represented bythe following Chemical Formula 2-1 or 2-2 depending on the position ofthe substituent.

in Chemical Formulae 2-1 to 2-2, R″₁, R″₂, and R″₃ are as defined inChemical Formula 2.

In one embodiment, the citrate-based compound may be at least oneselected from the group consisting of triethyl citrate, acetyl triethylcitrate, tributyl citrate, acetyl tributyl citrate, trioctyl citrate,acetyl trioctyl citrate, trihexyl citrate, and acetyl trihexyl citrate.

Preferably, the citrate-based compound may be at least one selected fromthe group consisting of tributyl citrate and acetyl tributyl citrate.

The tributyl citrate or acetyl tributyl citrate has low viscosity atroom temperature and low temperatures to realize excellent coatingproperties, has a fast gelling rate, and has better plasticizationefficiency and plasticizer migration resistance than other cyclohexanedicarboxylate-based compounds. Accordingly, when tributyl citrate oracetyl tributyl citrate is used, physical properties of the plasticizercomposition can be further improved while supplementing color and odorproblems caused by the recycled phthalate-based compound.

A citrate-based plasticizer other than the above tributyl citrate oracetyl tributyl citrate can also be used. However, if its molecularweight is high, processing may not be smooth due to the high viscosityand the slow gelling rate. And if its molecular weight is low, theplasticizer volatilizes during processing, causing contamination of theprocessing equipment as well as lowering physical properties of finalproducts.

The second plasticizer may be included in an amount of 10 parts byweight or more, 12 parts by weight or more, 15 parts by weight or more,18 parts by weight or more, or 20 parts by weight or more, and 85 partsby weight or less, preferably 80 parts by weight or less, 75 parts byweight or less, 70 parts by weight or less, 65 parts by weight or less,60 parts by weight or less, 55 parts by weight or less, or 50 parts byweight or less based on 100 parts by weight of the plasticizercomposition.

When the content of the second plasticizer is less than 10 parts byweight based on 100 parts by weight of the plasticizer composition, itmay be insufficient to supplement the physical properties of therecycled phthalate-based compound. In addition, when the content of thesecond plasticizer exceeds 85 parts by weight based on 100 parts byweight of the plasticizer composition, it is difficult to expect aneffect of reducing carbon emissions by the use of recycled rawmaterials.

In one embodiment of the present disclosure, the first plasticizer maybe recycled dioctyl terephthalate, and the second plasticizer may be atleast one selected from the group consisting of tributyl citrate andacetyl tributyl citrate.

According to one embodiment of the present disclosure, the plasticizercomposition may not include other plasticizers other than theabove-described first and second plasticizers.

Specifically, the plasticizer composition may include 15 to 90 parts byweight of recycled dioctyl terephthalate as the first plasticizer and 85to 10 parts by weight of at least one selected from the group consistingof tributyl citrate and acetyl tributyl citrate as the secondplasticizer.

Preferably, the plasticizer composition may include 30 to 85 parts byweight of recycled dioctyl terephthalate as the first plasticizer and 70to 15 parts by weight of at least one selected from the group consistingof tributyl citrate and acetyl tributyl citrate as the secondplasticizer.

More preferably, the plasticizer composition may include 50 to 80 partsby weight of recycled dioctyl terephthalate as the first plasticizer and50 to 20 parts by weight of at least one selected from the groupconsisting of tributyl citrate and acetyl tributyl citrate as the secondplasticizer.

Additional Plasticizer

Meanwhile, according to another embodiment of the present disclosure,the plasticizer composition may further include an additionalplasticizer in addition to the first and second plasticizers.

As the additional plasticizer, a material usually used as a plasticizerof a polymer resin may be used without limitation. For example, at leastone selected from the group consisting of trimellitate-based compounds,aliphatic ester-based compounds, and epoxidized vegetable oils may beused.

Specific example of the trimellitate-based compound may be at least oneselected from the group consisting of tri-(2-ethylhexyl) trimellitate,trimethyl trimellitate, trihexyl trimellitate, triheptyl trimellitate,tri-(n-octyl, n-decyl) trimellitate, and tri-(heptyl, nonyl)trimellitate.

The aliphatic ester-based compound may be an ester compound derived froman aliphatic carboxylic acid compound such as adipic acid, sebacic acid,azelaic acid, and maleic acid. Specific example of the aliphatic estercompound may be at least one selected from the group consisting ofdimethyl adipate, monomethyl adipate, dioctyl adipate, diheptylnonyladipate, di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyladipate, di(2-ethylhexyl)sebacate, dibutyl sebacate,di(2-ethylhexyl)azelate, dibutyl maleate, and diisobutyl maleate.

The epoxidized vegetable oil is epoxidized fatty acid alkyl estersprepared by epoxidizing fatty acid alkyl esters. For example, specificexample of the epoxidized vegetable oil may be at least one selectedfrom the group consisting of epoxidized soybean oil, epoxidized castoroil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate,epoxidized oleate, epoxidized tall oil, and epoxidized linoleate.

The additional plasticizer may be used alone or in combination of two ormore. According to a preferred embodiment, when the epoxidized vegetableoil is mixed as the plasticizer, thermal stability and flexibility ofthe product can be further improved, and when the trimellitate-basedcompound is mixed, volatility resistance can be further improved.

When the additional plasticizer is included, the content of theadditional plasticizer may be 1 part by weight or more, or 5 parts byweight or more, and 30 parts by weight or less, 20 parts by weight orless, or 10 parts by weight or less based on 100 parts by weight of theplasticizer composition. When the content of the additional plasticizeris too high, the content of the first and the second plasticizers isrelatively reduced. Therefore, the effect of securing a fast gellingrate and low plasticizer migration characteristics together with theabove-described carbon emission reduction effect and excellentplasticization efficiency cannot be sufficiently obtained, and thus itis preferable to satisfy the above range.

As described above, the plasticizer composition of the presentdisclosure includes the citrate-based compound together with therecycled phthalate-based compound, and thus has excellent color, lowodor, and a relatively low acid value even when the recycled rawmaterial is used.

Specifically, the plasticizer composition may have an acid value of 0.2KOH mg/g or less, 0.15 KOH mg/g or less, or 0.12 KOH mg/g or less. Thereis no specific lower limit, because the lower acid value can beevaluated as the better. In theory, the lower limit may be 0 KOH mg/g.In particular, the high acid value of the plasticizer composition meansthat there are many impurities in addition to the plasticizer. Whenthere are many impurities, the color of the plasticizer may change fromcolorless and transparent to yellow or brown, or the odor may be severe.Alternatively, migration resistance of the final product using theplasticizer having a high acid value may deteriorate. Thus, it ispreferable that the plasticizer composition maintains the acid valuewithin the above range.

In addition, the plasticizer composition may have a yellow index of 120or less, 100 or less, or 90 or less, when measured according to ASTMD1209 and E313.

In addition, the plasticizer composition may have a carbon emissionreduction rate of 5% or more, or 5% or more and 40% or less. The carbonemission reduction rate of the plasticizer composition is a valuecalculated in comparison with a plasticizer composition containing apure phthalate-based compound instead of the recycled phthalate-basedcompound, and corresponds to the carbon emission reduction rate with theuse of R-DOTP instead of pure DOTP.

Specifically, the carbon emission reduction rate (%) of the plasticizercomposition can be calculated as in Equation 1 below.

Carbon emission reduction rate (%)=100−[(A1/A2)×100]  [Equation 1]

In Equation 1,

A1 represents carbon emissions (tCO₂ eq/MT) with respect to aplasticizer composition according to the present disclosure, and

A2 represents carbon emissions (tCO₂ eq/MT) with respect to a controlplasticizer composition.

Specifically, A1 corresponds to total carbon emissions (tCO₂ eq/MT)according to the composition ratio of each component contained in theplasticizer composition. A2 corresponds to total carbon emissions (tCO₂eq/MT) according to the composition ratio of each component of a controlplasticizer composition using the same composition as the plasticizercomposition measured in A1, but containing a pure recycled phthalatecompound (pure-DOTP) instead of the recycled phthalate-based compound(R-DOTP). Herein, the unit of the carbon emissions is a weightequivalent (eq) of total CO₂ emissions per metric ton.

For example, the carbon emissions (A1) with respect to the plasticizercomposition containing R-DOTP and TBC at 80:20 is 0.502 tCO₂ eq/MTcalculated as the sum of carbon emissions of each component according tothis composition ratio, that is, carbon emissions of R-DOTP×0.8+carbonemissions of TBC×0.2. The control plasticizer composition with respectto the above plasticizer composition is a plasticizer compositioncontaining DOTP and TBC at 80:20, and the carbon emissions (A2) thereofis 0.571 tCO₂ eq/MT calculated as carbon emissions of DOTP×0.8+carbonemissions of TBC×0.2. Therefore, according to Equation 1, the carbonemission reduction rate of the plasticizer composition containing R-DOTPand TBC at 80:20 is 12.08%.

At this time, the carbon emissions of each component used in theplasticizer composition is as follows:

Recycled dioctyl terephthalate (R-DOTP): 0.485 tCO₂ eq/MT

Pure dioctyl terephthalate (DOTP, or Pure-DOTP): 0.571 tCO₂ eq/MT

Tributyl citrate (TBC): 0.571 tCO₂ eq/MT

The carbon emissions of each component used in the plasticizercomposition may refer to the value provided by the manufacturer or maybe calculated based on the manufacturing process and chemical reactionof each component. A method of calculating the carbon emission reductionrate may be specified in Experimental Example to be described later.

For example, the reduction amount of carbon emissions by using R-DOTP is0.086 tCO₂ eq/MT. [0.571(Pure DOTP)−0.485(R-DOTP)=0.086(15.06%)]. Thecarbon emissions of pure DOTP can be calculated as 0.571 tCO₂ eq/MT andthat of R-DOTP can be calculated as 0.485 tCO₂ eq/MT.

Preferably, the carbon emission reduction rate of the plasticizercomposition may be 5.5% or more, 5.8% or more, 6% or more, 6.5% or more,6.8% or more, 7% or more, or 7.5% or more. However, considering theactual carbon emissions according to each component of the plasticizer,it may be 40% or less, 30% or less, 25% or less, 20% or less, 18% orless, or 16% or less.

Meanwhile, the plasticizer composition is excellent in physicalproperties such as gelling properties, plasticization efficiency, andweather resistance when used with a resin. Therefore, the plasticizercomposition of the present disclosure can be applied to various polymerresins as a plasticizer.

Resin Composition

Accordingly, according to another embodiment of the present disclosure,there is provided a resin composition including the plasticizercomposition; and at least one resin selected from the group consistingof polyvinyl chloride, polystyrene, polyurethane, polypropylene,polybutadiene, silicone, modified silicone, ethylene vinyl acetateresin, and thermoplastic elastomer.

The contents of the resin and the plasticizer in the resin compositionare not limited, and may be appropriately adjusted depending on theresin used and the desired physical properties. For example, the resincomposition may include 1 to 200 parts by weight, 10 to 150 parts byweight, 20 to 120 parts by weight, or 30 to 80 parts by weight of theabove-described plasticizer composition based on 100 parts by weight ofthe resin.

The resin composition may further include at least one additive selectedfrom the group consisting of stabilizers, fillers and pigments. Theadditive may be appropriately selected depending on physical propertiesto be improved in the resin composition.

The stabilizer is added for the purpose of preventing changes in thephysical properties of the resin, and includes at least one selectedfrom the group consisting of Ca—Zn-based compounds, K—Zn-basedcompounds, Ba—Zn-based compounds, organic Tin-based compounds; metallicsoap-based compounds, phenol-based compounds, phosphoric acidester-based compounds and phosphorous acid ester-based compounds.

More specific examples of the stabilizers which may be used in thepresent disclosure may include Ca—Zn-based compounds; K—Zn-basedcompounds; Ba—Zn-based compounds; organic Tin-based compounds such asmercaptide-based compounds, maleic acid-based compounds or carboxylicacid-based compounds; metallic soap-based compounds such as Mg-stearate,Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; phenol-basedcompounds; phosphoric acid ester-based compounds; phosphorous acidester-based compounds, etc., but the present disclosure is not limitedthereto.

The filler is used for the purpose of improving productivity, dry touchfeeling, and flame retardant properties of the resin composition, andincludes at least one selected from the group consisting of calciumcarbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesiumhydroxide, aluminum hydroxide, phosphorus-based compounds,melamine-based compounds, phosphorus-melamine complex compounds,boron-based flame retardants, carbon black, carbon nanotube, nano-clay,and clay.

The pigment may be titanium dioxide, carbon black, cadmium-basedpigment, or the like.

The resin composition according to the present disclosure may beprepared according to a method commonly known in the art by using theresin, the plasticizer composition, and optionally, the additive. Themethod is not particularly limited.

In one embodiment, the resin composition may be a vinyl chloride resincomposition including a vinyl chloride resin. The vinyl chloride resincomposition includes the plasticizer composition according to thepresent disclosure, thereby exhibiting excellent color, gellingproperties and weather resistance.

The vinyl chloride resin may be a homopolymer in which a vinyl chloridemonomer is homopolymerized, or a copolymer in which a vinyl chloridemonomer and a comonomer copolymerizable therewith are polymerized. Anyone or a mixture thereof may be used in the preparation of the vinylchloride resin composition.

The comonomer copolymerizable with the vinyl chloride monomer may be,specifically, vinyl esters such as vinyl acetate, vinyl propionate, orvinyl stearate; vinyl ethers having an alkyl group such as methyl vinylether, ethyl vinyl ether, octyl vinyl ether, or launyl vinyl ether;vinylidene halides such as vinylidene chloride; unsaturated carboxylicacids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid,itaconic acid, maleic anhydride, or itaconic anhydride, and acidanhydrides thereof; unsaturated carboxylic acid esters such as methylacrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, orbutylbenzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, or divinyl benzene; unsaturated nitriles such as acrylonitrileor methacrylonitrile; olefins such as ethylene or propylene; orcross-linkable monomers such as diallyl phthalate. Any one or a mixtureof two or more thereof may be used. Among them, the comonomer may morepreferably include vinyl acetate, etc. in terms of excellentcompatibility with the vinyl chloride monomer and improvingcompatibility with the plasticizer constituting the resin compositionafter polymerization.

As described above, the vinyl chloride resin may be prepared bypolymerization of a vinyl chloride monomer alone, or by polymerizationof a vinyl chloride monomer and a comonomer copolymerizable therewith.At this time, the polymerization method is not particularly limited, andthe polymerization may be performed according to a conventionalpolymerization method known in the art such as suspensionpolymerization, bulk polymerization, emulsion polymerization, or seedemulsion polymerization.

The average particle size and uniformity of the vinyl chloride resin canbe controlled by adjusting the polymerization conditions. Specifically,the straight vinyl chloride resin prepared by suspension polymerizationor bulk polymerization may have an average particle size (D₅₀) of 50 μmto 400 μm, and the paste vinyl chloride resin prepared by emulsionpolymerization or fine suspension polymerization may have an averageparticle size (D₅₀) of less than 100 μm, preferably 0.1 μm to 40 μm. Theaverage particle size (D₅₀) of the vinyl chloride resin may be measuredaccording to a conventional particle size distribution measuring methodsuch as optical microscopy or light scattering measurement.

A bulk density of the vinyl chloride resin measured according to ASTM D1895 may be in the range of 0.1 g/cm³ to 0.5 g/cm³, or 0.2 g/cm³ tog/cm³. The plasticizer absorption effect may be excellent within theabove bulk density range.

The degree of polymerization and the weight average molecular weight ofthe vinyl chloride resin may affect compatibility with the componentsconstituting the vinyl chloride resin composition, particularly aplasticizer, and processability of the vinyl chloride resin composition,and may be appropriately adjusted by controlling polymerizationconditions during polymerization.

Specifically, the vinyl chloride resin may have the degree ofpolymerization of 500 to 3,000, or the weight average molecular weight(Mw) of 25,000 g/mol to 300,000 g/mol. When the degree of polymerizationand the weight average molecular weight are within the above ranges,dispersibility is excellent, compatibility with the plasticizer is good,and processability of the vinyl chloride resin composition can beimproved.

If the degree of polymerization of the vinyl chloride resin is less than500 or the weight average molecular weight is less than 25,000 g/mol,there is a fear that processability and durability of the product afterprocessing may be deteriorated due to insufficient physical properties.When the degree of polymerization is more than 3,000 or the weightaverage molecular weight is more than 300,000 g/mol, the molecularweight is too high, thereby making it difficult to mold or process. Morespecifically, the vinyl chloride resin may have the degree ofpolymerization of 700 or more and less than 1,700 or the weight averagemolecular weight (Mw) of 45,000 g/mol to 250,000 g/mol.

The weight average molecular weight (Mw) of the vinyl chloride resin isa converted value using standard polystyrene by gel permeationchromatography. In addition, the degree of polymerization of the vinylchloride resin can be measured according to JIS K 6720-2.

Meanwhile, the resin composition may have an acid value of 0.2 KOH mg/gor less, 0.15 KOH mg/g or less, or 0.12 KOH mg/g or less. There is nospecific lower limit, because the lower acid value can be evaluated asthe better. In theory, the lower limit may be 0 KOH mg/g.

In addition, the resin composition may have a yellow index (YI) measuredaccording to ASTM E313 of 8 to 19, 9 to 18, 10 to 17, or 11 to 17.

In addition, the resin composition may have a yellow index (YI) measuredafter 200 hours of UV aging according to ASTM G154 Cycle 2 method of 5to 18, 6 to 18, 7 to 17, or 10 to 16.

In addition, the resin composition may have a carbon emission reductionrate of 3% or more, or 3% or more and 30% or less. The carbon emissionreduction rate of the resin composition is a value calculated incomparison with a vinyl chloride resin composition using a plasticizercomposition containing a pure phthalate-based compound instead of therecycled phthalate-based compound, and corresponds to the carbonemission reduction rate with the use of R-DOTP instead of pure DOTP.

Specifically, the carbon emission reduction rate (%) of the resincomposition can be calculated as in Equation 2 below.

Carbon emission reduction rate (%)=100−[(A3/A4)×100]  [Equation 2]

In Equation 2,

A3 represents carbon emissions (tCO₂ eq/MT) with respect to a resincomposition according to the present disclosure, and

A4 represents carbon emissions (tCO₂ eq/MT) with respect to a controlresin composition.

Specifically, A3 corresponds to total carbon emissions (tCO₂ eq/MT)according to the composition ratio of each component contained in theresin composition. A4 corresponds to total carbon emissions (tCO₂ eq/MT)according to the composition ratio of each component of the resincomposition using a plasticizer composition using the same compositionas the resin composition measured in A3, but containing a pure recycledphthalate compound (pure-DOTP) instead of the recycled phthalate-basedcompound (R-DOTP). Herein, the unit of the carbon emissions is a weightequivalent (eq) of total CO₂ emissions per metric ton.

For example, when the resin composition is a vinyl chloride resincomposition using 100 parts by weight of polyvinyl chloride (PVC) and 30parts by weight of a plasticizer containing R-DOTP and TBC at 80:20, thecarbon emissions (A3) of the resin composition is calculated as the sumof carbon emissions of each component according to the composition ratiowith the weight ratio of PVC, R-DOTP, and TBC of 0.769, 0.185, and0.046, and is 0.256 tCO₂ eq/MT (that is, carbon emissions ofPVC×0.769+carbon emissions of R-DOTP×0.185+carbon emissions ofTBC×0.046). The control resin composition with respect to the abovevinyl chloride resin composition is a resin composition containing PVC,DOTP, and TBC at a weight ratio of 0.769, 0.185, and 0.046, and thecarbon emissions (A4) thereof is 0.271 tCO₂ eq/MT calculated as carbonemissions of PVC×0.769+carbon emissions of DOTP×0.185+carbon emissionsof TBC×0.046. Therefore, according to Equation 2, the carbon emissionreduction rate of the vinyl chloride resin composition is 5.54%.

At this time, the carbon emissions of each component used in the resincomposition is as follows:

Polyvinyl chloride (PVC, Hanwha Solutions P-1000, degree ofpolymerization of 1000): 0.182 tCO₂ eq/MT

Recycled dioctyl terephthalate (R-DOTP): 0.485 tCO₂ eq/MT

Pure dioctyl terephthalate (DOTP, or Pure-DOTP): 0.571 tCO₂ eq/MT

Tributyl citrate (TBC): 0.571 tCO₂ eq/MT

The carbon emissions of each component used in the resin composition mayrefer to the value provided by the manufacturer or may be calculatedbased on the manufacturing process and chemical reaction of eachcomponent. A method of calculating the carbon emission reduction ratemay be specified in Experimental Example to be described later.

Preferably, the carbon emission reduction rate of the resin compositionmay be 3.2% or more, 3.5% or more, 4% or more, 4.5% or more, 5% or more,5.5% or more, 6% or more, or 6.5% or more. However, considering theactual carbon emissions according to each component of the plasticizer,it may be 28% or less, 25% or less, 22% or less, 20% or less, 18% orless, or 16% or less.

In addition, the resin composition has excellent color and odorcharacteristics as described above, and also has excellentplasticization efficiency and a fast gelling rate.

For example, when 50 g to 58 g of the resin composition is put into aBrabender Mixer at a temperature of 90° C. to 98° C. and mixed at 25 rpmto 35 rpm for 10 minutes, a gelling time (sec) of the resin measured bychanging the torque in the mixer during processing may be 130 seconds orless, or 10 seconds to 130 seconds. The method for measuring the gellingrate may be more specifically described in Experimental Exampledescribed below. Preferably, the gelling time of the resin compositionmay be 125 seconds or less, 120 seconds or less, 118 seconds or less,115 seconds or less, or 110 seconds or less. However, considering theactual gelation process of the general resin composition, the gellingtime of the resin composition may be 20 seconds or more, 30 seconds ormore, 40 seconds or more, 50 seconds or more, or 60 seconds or more.

According to another aspect of the present disclosure, there is provideda molded product including the above resin composition.

The molded product may be used in the manufacture of a food packagingfilm (e.g., wrap), industrial film, compound, decor sheet, decor tile,soft sheet, hard sheet, wire and cable, wallpaper, foam mat, artificialleather, flooring, tarpaulin, gloves, sealant, gasket of refrigerator,hoses, medical device, geogrids, mesh tarpaulin, toy product,stationery, insulating tape, clothing coatings, label used for clothingor stationery, bottle cap liner, stopper for industrial or otherpurposes, artificial bait, electronic component (e.g., sleeve),automobile interior material, adhesive, coatings, and the like, but thepresent disclosure is not limited thereto.

Hereinafter, the present invention will be described in more detail withthe following examples. However, the following examples are only forillustrating the present invention, and the scope of the presentinvention is not limited thereto.

EXAMPLES Example 1

A plasticizer composition was prepared by mixing recycled dioctylterephthalate (R-DOTP, acid value of 0.175 KOH mg/g) manufactured byRunzenengyuan of China and tributyl citrate (TBC) at a weight ratio of80:20.

30 parts by weight of the plasticizer composition and 1.5 parts byweight of a Ba/Zn-based thermal stabilizer (Songwon Industrial BZ-150T)were added based on 100 parts by weight of polyvinyl chloride (PVC,Hanwha Solutions P-1000, degree of polymerization of 1000), and thenkneaded with a roll mill to prepare a vinyl chloride resin composition.

Example 2

A plasticizer composition was prepared by mixing recycled dioctylterephthalate (R-DOTP, acid value of 0.175 KOH mg/g) manufactured byRunzenengyuan of China and tributyl citrate (TBC) at a weight ratio of50:50.

30 parts by weight of the plasticizer composition and 1.5 parts byweight of a Ba/Zn-based thermal stabilizer (Songwon Industrial BZ-150T)were added based on 100 parts by weight of polyvinyl chloride (PVC,Hanwha Solutions P-1000, degree of polymerization of 1000), and thenkneaded with a roll mill to prepare a vinyl chloride resin composition.

Example 3

A vinyl chloride resin composition was prepared in the same manner as inExample 1, except that 50 parts by weight of the plasticizer compositionwas added based on 100 parts by weight of polyvinyl chloride (PVC,Hanwha Solutions P-1000, degree of polymerization of 1000).

Example 4

A vinyl chloride resin composition was prepared in the same manner as inExample 2, except that 50 parts by weight of the plasticizer compositionwas added based on 100 parts by weight of polyvinyl chloride (PVC,Hanwha Solutions P-1000, degree of polymerization of 1000).

Comparative Example 1

A vinyl chloride resin composition was prepared in the same manner as inExample 1, except for using recycled dioctyl terephthalate (R-DOTP)manufactured by Runzenengyuan of China as a single componentplasticizer.

Comparative Example 2

A vinyl chloride resin composition was prepared in the same manner as inComparative Example 1, except that pure dioctyl terephthalate (DOTP) wasused as a plasticizer instead of recycled dioctyl terephthalate.

Comparative Example 3

A vinyl chloride resin composition was prepared in the same manner as inComparative Example 1, except for using tributyl citrate (TBC) as asingle component plasticizer.

Comparative Example 4

A plasticizer composition and a vinyl chloride resin composition wereprepared in the same manner as in Example 1, except that pure dioctylterephthalate (DOTP) was used instead of recycled dioctyl terephthalate.

Comparative Example 5

A plasticizer composition and a vinyl chloride resin composition wereprepared in the same manner as in Example 2, except that pure dioctylterephthalate (DOTP) was used instead of recycled dioctyl terephthalate.

Comparative Example 6

A plasticizer composition and a vinyl chloride resin composition wereprepared in the same manner as in Example 3, except that pure dioctylterephthalate (DOTP) was used instead of recycled dioctyl terephthalate.

Comparative Example 7

A plasticizer composition and a vinyl chloride resin composition wereprepared in the same manner as in Example 4, except that pure dioctylterephthalate (DOTP) was used instead of recycled dioctyl terephthalate.

Experimental Examples

Each of the plasticizer compositions and the vinyl chloride resincompositions of Examples and Comparative Examples was evaluated by thefollowing method, and the results are shown in Table 1.

(1) Carbon Emission Reduction Rate (%)

Carbon emission reduction rates (%) with respect to the plasticizercompositions of Examples and Comparative Examples were calculatedaccording to Equation 1 below.

Carbon emission reduction rate (%)=100−[(A1/A2)×100]  [Equation 1]

In Equation 1,

A1 represents carbon emissions (tCO₂ eq/MT) with respect to aplasticizer composition, and

A2 represents carbon emissions (tCO₂ eq/MT) with respect to a controlplasticizer composition.

Specifically, in Equation 1, A1 corresponds to total carbon emissions(tCO₂ eq/MT) according to the composition ratio of each componentcontained in the plasticizer composition. A2 corresponds to total carbonemissions (tCO₂ eq/MT) according to the composition ratio of eachcomponent of a control plasticizer composition using the samecomposition as the plasticizer composition measured in A1, butcontaining a pure recycled phthalate compound (pure-DOTP) instead of therecycled phthalate-based compound (R-DOTP). Herein, the unit of thecarbon emissions is a weight equivalent (eq) of total CO₂ emissions permetric ton.

In addition, carbon emission reduction rates (%) with respect to thevinyl chloride resin compositions of Examples and Comparative Exampleswere calculated according to Equation 2 below.

Carbon emission reduction rate (%)=100−[(A3/A4)×100]  [Equation 2]

In Equation 2,

A3 represents carbon emissions (tCO₂ eq/MT) with respect to a resincomposition, and

A4 represents carbon emissions (tCO₂ eq/MT) with respect to a controlresin composition.

Specifically, in Equation 2, A3 corresponds to total carbon emissions(tCO₂ eq/MT) according to the composition ratio of each componentcontained in the resin composition. A4 corresponds to total carbonemissions (tCO₂ eq/MT) according to the composition ratio of eachcomponent of the resin composition using a plasticizer composition usingthe same composition as the resin composition measured in A3, butcontaining a pure recycled phthalate compound (pure-DOTP) instead of therecycled phthalate-based compound (R-DOTP). Herein, the unit of thecarbon emissions is a weight equivalent (eq) of total CO₂ emissions permetric ton.

For example, the carbon emissions (A1) with respect to the plasticizercomposition of Example 1 containing R-DOTP and TBC at 80:20 is 0.502tCO₂ eq/MT calculated as the sum of carbon emissions of each componentaccording to this composition ratio. In addition, the carbon emissions(A3) with respect to the vinyl chloride resin composition of Example 1is 0.256 tCO₂ eq/MT calculated as the sum of carbon emissions of eachcomponent according to this composition ratio, wherein the vinylchloride resin composition uses 30 parts by weight of the plasticizercontaining R-DOTP and TBC at 80:20 with 100 parts by weight of polyvinylchloride (PVC), and the composition of each component PVC, R-DOTP, andTBC contained in the vinyl chloride resin composition has a weight ratioof 0.769, 0.185, and 0.046.

At this time, the carbon emissions of each component used in theplasticizer composition and the vinyl chloride resin composition ofExamples and Comparative Examples is as follows:

Polyvinyl chloride (PVC, Hanwha Solutions P-1000, degree ofpolymerization of 1000): 0.182 tCO₂ eq/MT

Recycled dioctyl terephthalate (R-DOTP): 0.485 tCO₂ eq/MT

Pure dioctyl terephthalate (DOTP, or Pure-DOTP): 0.571 tCO₂ eq/MT

Tributyl citrate (TBC): 0.571 tCO₂ eq/MT

Among them, the carbon emissions of polyvinyl chloride (PVC) and puredioctyl terephthalate (DOTP, or Pure-DOTP) referred to the valueprovided by the manufacturer. In addition, the carbon emissions of theheat stabilizer added in a relatively small amount in the resincomposition was excluded. In addition, the carbon emissions of recycleddioctyl terephthalate (R-DOTP) was calculated assuming that the carbonemissions of recycled PTA used for R-DOTP is 70% of that of pure PTA,and the carbon emissions of PTA and the carbon emissions of 2-EH are thesame. PTA (pured terephthalic acid) and 2-EH (2-ethylhexanol) are rawmaterials for manufacturing DOTP. In addition, the carbon emissions oftributyl citrate (TBC) was calculated assuming that the carbon emissionsof TBC produced by a chemical reaction similar to that of Pure-DOTP isthe same as the carbon emissions of Pure-DOTP.

In addition, the reduction amount of carbon emissions by using R-DOTP is0.086 tCO₂ eq/MT. [0.571(Pure DOTP)−0.485(R-DOTP)=0.086(15.06%)]. Thecarbon emissions of pure DOTP can be calculated as 0.571 tCO₂ eq/MT andthat of R-DOTP can be calculated as 0.485 tCO₂ eq/MT.

(2) Volatile Loss (%)

20 g of each of the prepared plasticizer compositions was placed in aglass Petri dish (diameter of 90 mm), and the amount of volatilizedplasticizer at 200° C. for 1 hour was measured. The volatile loss wascalculated according to Equation 3 below.

Volatile loss (%)=[(weight of plasticizer after test)/(weight ofplasticizer before test)]×100  [Equation 3]

(3) Color Evaluation

A flat sheet having a thickness of about 2 mm was prepared bysequentially performing roll mill processing (170° C., 3 minutes) andpress processing (180° C., 8 minutes) on the vinyl chloride resincomposition.

For the specimen prepared above, a yellow index (YI) was measuredaccording to ASTM E313.

(4) Odor Evaluation

Odor evaluation for the prepared plasticizer composition was performedby a sensory evaluation. The odor of the plasticizer composition wasscored from the lowest score of 1 to the highest score of 5 with thetrend of reduction of odors such as oil. That is, the odor evaluationwas expressed as 5 (excellent, excellent without odor)>4>3 (good)>2>1(very poor, bad odor). When manufacturing the final resin product, itshould be grade 3 or higher in terms of preventing quality deteriorationdue to odor problems caused by plasticizers.

(4) Gelling Rate

54 g of the vinyl chloride resin composition was put into a BrabenderMixer at 95° C., and mixed at 30 rpm for 10 minutes. The gelling time(sec) of the resin was analyzed by changing the torque in the mixerduring processing.

(5) Plasticizer Migration Resistance (%)

A flat sheet having a thickness of about 2 mm was prepared bysequentially performing roll mill processing (170° C., 3 minutes) andpress processing (180° C., 8 minutes) on the vinyl chloride resincomposition, and the prepared sheet was cut into a circular specimenhaving a diameter of about 4 cm. An oil-absorbing paper made ofpolypropylene was placed on the upper/lower part of the specimen andleft at 60° C. under a load of 5 kg for 7 days to promote plasticizermigration. After the plasticizer migration experiment was completed, theweight change rates of the specimen and the oil paper were measured.

The weight change rate of the specimen was calculated as [(weight changeof specimen/weight of specimen before test)×100], and the weight changerate of oil paper was calculated as [(weight change of oil paper/weightof oil paper before test)×100]. The weight loss of the specimen is thesame as the weight gain of the oil paper, so in this experiment,plasticizer migration resistance (%) was evaluated only with the weightchange rate of the specimen.

(6) Hardness (Plasticization Efficiency)

A flat sheet having a thickness of about 2 mm was prepared bysequentially performing roll mill processing (170° C., 3 minutes) andpress processing (180° C., 8 minutes) on the vinyl chloride resincomposition.

Based on the ASTM D2240 method, a needle of a hardness tester (Type A)was completely lowered to one place of the specimen to read a hardnessvalue after 5 seconds. After testing three places for each specimen, theaverage value thereof was taken. The measured hardness value is used asan index indicating the plasticization efficiency.

TABLE 1 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex.4 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Plasticizer R-DOTP/ R-DOTP/R-DOTP/ R-DOTP/ R-DOTP Pure- TBC DOTP/ DOTP/ DOTP/ DOTP/ composition TBCTBC TBC TBC DOTP TBC TBC TBC TBC (8:2) (5:5) (8:2) (5:5) (8:2) (5:5)(8:2) (5:5) PVC content 100 100 100 100 100 100 100 100 100 100 100(parts by weight) Plasticizer 30 30 50 50 30 30 30 30 30 50 50 content(parts by weight) Carbon 0.502 0.529 0.502 0.529 0.485 0.571 0.571 0.5710.572 0.571 0.572 emissions of plasticizer composition (tCO2 eq/MT)Carbon 12.08 7.52 12.08 7.52 15.06 0 0 0 0 0 0 emission reduction rateof plasticizer composition (%) Carbon 0.256 0.262 0.288 0.297 0.2520.272 0.272 0.271 0.272 0.311 0.311 emissions of vinyl chloride resincomposition (tCO2 eq/MT) Carbon 5.54 3.68 7.40 4.50 7.35 0 0 0 0 0 0emission reduction rate of vinyl chloride resin composition (%) Volatile1.9 2.2 1.9 2.2 1.5 1.2 2.9 1.7 2.0 1.7 2.1 loss of plasticizer (%)Initial 17 15 13 11 23 17 13 16 12 13 11 coloration (Color, YI) Odorgrade 3 4 3 4 1 4 4 4 5 4 5 Gelling time 110 98 88 61 170 168 80 112 10187 62 (sec) Plasticizer 0.5 0.8 0.3 0.4 1.4 1.4 0.2 0.5 0.8 0.3 0.4migration (%) Hardness 86 85 64 62 88 88 85 85 84 65 61 (Shore A)

Referring to Table 1, it was confirmed that the plasticizer compositionof the present disclosure had good odor and excellent color evenincluding the recycled phthalate-based compound, and exhibited a fastgelling rate and low plasticizer migration characteristics with highplasticization efficiency.

1. A plasticizer composition, comprising a) a recycled phthalate-basedcompound as a first plasticizer; and b) a citrate-based compound as asecond plasticizer, wherein the first plasticizer is included in anamount of 90 parts by weight or less based on 100 parts by weight of theplasticizer composition.
 2. The plasticizer composition of claim 1,wherein 100 parts by weight of the plasticizer composition comprises 15to 90 parts by weight of the first plasticizer, and 10 to 85 parts byweight of the second plasticizer.
 3. The plasticizer composition ofclaim 1, wherein the first plasticizer is at least one selected from thegroup consisting of recycled dibutyl phthalate, recycled dihexylphthalate, recycled dioctyl phthalate, recycled di-n-octyl phthalate,recycled diisononyl phthalate, recycled diisodecyl phthalate, recycleddibutyl isophthalate, recycled dioctyl isophthalate, recycled diisononylisophthalate, recycled diisodecyl isophthalate, recycled dibutylterephthalate, recycled dioctyl terephthalate, recycled diisononylterephthalate, and recycled diisodecyl terephthalate.
 4. The plasticizercomposition of claim 1, wherein the second plasticizer is at least oneselected from the group consisting of triethyl citrate, acetyl triethylcitrate, tributyl citrate, acetyl tributyl citrate, trioctyl citrate,acetyl trioctyl citrate, trihexyl citrate, and acetyl trihexyl citrate.5. The plasticizer composition of claim 1, wherein the first plasticizeris recycled dioctylterephthalate; and the second plasticizer is at leastone selected from the group consisting of tributyl citrate, and acetyltributyl citrate.
 6. The plasticizer composition of claim 1, wherein thefirst plasticizer has an acid value of 0.2 KOH mg/g or less.
 7. Theplasticizer composition of claim 1, further comprising at least onecompound selected from the group consisting of trimellitate-basedcompounds, aliphatic ester-based compounds, and epoxidized vegetableoils.
 8. The plasticizer composition of claim 1, wherein carbon emissionreduction is 5% or more.
 9. A resin composition comprising theplasticizer composition of claim 1; and at least one resin selected fromthe group consisting of polyvinyl chloride, polystyrene, polyurethane,polypropylene, polybutadiene, silicone, modified silicone, ethylenevinyl acetate resin, and thermoplastic elastomer.
 10. The resincomposition of claim 9, wherein the plasticizer composition is includedin an amount of 1 part by weight to 200 parts by weight based on 100parts by weight of the resin.
 11. The resin composition of claim 9,wherein a yellow index (YI) measured according to ASTM E313 is 8 to 19.12. The resin composition of claim 9, wherein a yellow index (YI)measured after 200 hours of UV aging according to ASTM G154 Cycle 2method is 5 to
 18. 13. A molded product comprising the resin compositionof claim 9.